Polymeric materials from iso-and isothiocyanates with acrylic acids



Patented Jan. 18, 1949 POLYMERIC MATERIALS FROM 180- AND ISOTHIOCYANATESWITH ACRYLIC ACIDS Joy G. Lichty, Stow,.and Nelson V. Seeger, GuyahogaFalls, Ohio, assignors to Wlngfoot Corporation, Akron, Ohio, acorporation of Delaware No Drawing. Application September 16, 1943, a

Serial No. 502,634

7 Claims.

This invention relates to polymeric materials and a method for preparingthem.

It is known that high molecular Weight materials may be prepared byreacting a compound having a plurality of isocyanate or isothiocyanateradicals with a compound having a plurality of groups containingreplaceable hydrogen, such as polyamino compounds, polyhydroxycompounds, aminohydroxy compounds, polycarboxylic compounds and thelike. It has now been discovered thatorganic diisocyanates anddiisothiocyanates may be reacted with an acrylic acid which containsonly a single carboxyl group to produce high molecular weight polymericmaterials.

Since the diisocyanate (or diisothiocyanate) 1 dioxide W v th m i n fthe po yhas two equally reactive radicals while the amide was completeThe p t s C d acrylic acid has only one, the acrylicacid may t this t eresulting p d ct s a D 3- react with either or both of the isocyanate(or meric polyamide capable of forming rs- If isothiocyanate) radicals.Thus, the reaction will d sir d th resin m y be fi d y t u d beinfluenced in art by the proportions of reheating with "or With ut n oxyn-provi in actants, which will usually be employed in the catalyst. Thismodification can be carried out ratio of about one to two mols of theacrylic acid at pe t ranging from 6 0 C- to each mol of the diisocyanate(or diisothiocy- Example 3 anate) so as to avoid an undue excess ofeither reactant 5 Forty-nine grams (0.5 mol) of ethacrylic acid Itappears that the acrylic acid and and 82 grams (0.5 mol) ofhexamethylene diiso' anate react to form an addition product. Thus,cyante were miXFd, an reaction in some cases, when liquid reactants aremixed llquld was heated to t room temperature a solid form At some- 100C. and carbon dioxode was evolved. Itwas h t higher temperatures, forexample, at about then heated to 150-470; (3., further polymerization Cand higher oarbon dioxide is split out occurring. 0n cooling, a clear,soft, elastic solid and polymerization takes place. It is reasonwasObtained; H able to suppose that the final product is in the Any Orgemc'dllsocyanete 0r dllsothlocyanatenature of a po1yam1de either aliphaticor aromatic, may be employed in The temperature for the polymerizationmay the invention. Further representative examples be variedconsiderably. Satisfactory results are are Octamethylene diisocyanate,decajmethylene customarily obtained t a temperature of aboutdiisocyanate, ethylene diisocyanate, trimethylene 100.450 C Thepolymerization proceeds t diisocyanate and other alkylene diisocyanates,oxy t a catalyst t, if desired, an oxygen providing bis (trimethyleneisocyanate), ethylene bis (tripolymerization catalyst such as benzoylperoxide, 4() methylene y e methylene l -p acetyl peroxide, sodiumperoxide, sodium perboylene isocyanate), D,P' D y e dlls eya ete, rateand tertiary butyl chromate may be used. the Xylylene dlisqcyanates 'lmetaand Such catalysts, if used, are ordinarily employed D -Ph yi s eytes, etc. and the corin relatively small amount, for example, aboutrespomilng Q WP 0.5-4%. Moreover, .m addition to the parent acrylic Thepractice of the invention is illustrated by acid, subst tuted l e acidseontelning Verb the following examples: we substituents which are inertin the reaction may be employed. Further examples are Example 1c-methacrylic acid, a-ethacrylic acid and other A mixture of 84.8 grams(1.18 mol) of acrylic 5o alpha-alkyl acrylic acids, a-phIll/l acrylicacid, acid and 99 grams (0.59 mol) of hexamethylene a-chloroacrylicacid, a-bromoacrylic acid, e-methd y t was t d lly to 0 C- oxyacrylicacid, a, p-dichloroacrylic acid, etc. large evolution of carbon dioxidetook place, givw we olaim 8 a y Viscous liqllii After 8 short 1. Aprocess of forming a solid rubbery polytimled Peried f heating at theliquid 55 meric material which comprises reacting from polymerized toproduce, on cooling, an elastic, rubber-like material.

Example 2 product separating with little liberation of carbon dioxide.The temperature was raised to 180 C. for a period of 510 minutes. Heremuch carbon dioxide was evolved. Some solid still remained. Thetemperature was now increased to the melting point of the solid wheremore carbon dioxide was evolved. When no more carbon one to two mols ofa monomer group consisting of acrylic acid, alpha. methacrylic acid,alpha ethacrylic acid, alpha phenyl acrylic acid, alpha chloroacrylicacid, alpha bromoacrylic acid, alpha methoxyacrylic acid and alpha betadichloroacrylic acid with one mol of a material selected from the groupconsisting of organic diisocyanates having as the sole functionalconstituents two lsocyanate radicals and organic diisothiocyanateshaving as the sole functional constituents two isothiocyanate radicalsat a temperature between 100-150 C.

2. A process of forming a solid rubbery polymeric material whichcomprises reacting from one to two mols of acrylic acid with one mol ofa material selected from the group consisting of organic diisocyanateshaving as the sole functional constituents two isocyanate radicals andselected from the organic diisothiocyanates having as the sole solefunctional constituents two isocyanate radicals and organicdiisothiocyanates having as the sole functional constituents twoisothiocyanate radicals at a temperature between l00l50 C.

4. The process of forming a solid rubbery polymeric material whichcomprises reacting from one to two mols of a monomer selected from thegroup consisting of acrylic acid, alpha metha-' crylic acid, alphaethacrylic acid, alpha phenyl acrylic acid, alpha chloroacrylic acid,alpha bromoacrylic acid, alpha methoxyacrylic acid and alpha betadichloroacrylic acid with one mol of hexamethylene' diisocyanate at atemperature between -150 C.

5. The process of forming a solid rubbery polymeric material whichcomprises reacting from one to two mols of acrylic acid with one mol ofhexamethylene diisocyanate at a temperature between 100-150 C.

6. The process of forming a solid rubbery polymeric material whichcomprises reacting from one to two mols of methacrylic acid withtone molof hexamethylene dlisocyanate at a temperature between 100-150 C.

'7. The process of forming a solid rubbery polymeric material whichcomprises reacting from one to two mols of ethacrylic acid with one molof hexamethylene diisocyanate at a temperature The following referencesare of record in the file of this patent:

UNITED STATES PATENTS Name Date Hanford et al. June 2, 1942 Number

